Liquid crystalline polyesters and methods for their production

ABSTRACT

A liquid crystalline polyester comprising dicarboxylic acid units of the following formula (1): ##STR1## wherein R 1  is a bivalent aromatic hydrocarbon group having from 6 to 18 carbon atoms, diol units of the following formula (2): 
     
         --OCH.sub.2 CH.sub.2 O--                                   (2) 
    
     and p-oxybenzoic acid units of the following formula (3): ##STR2##

The present invention relates to novel liquid crystalline polyesterswherein the sequence is alternately controlled and methods for theirproduction. The liquid crystalline polyesters of the present inventionhave not only high modulus of elasticity, high tensile strength, highflexural strength and high impact strength but also a high level ofelongation, and they are tough. Further, with the same composition andthe same compositional ratio, they are superior to conventional productsnot only in the mechanical properties but also in heat resistance. Theliquid crystalline polyesters of the present invention exhibit thesecharacteristics, as they form thermotropic liquid crystals during themolding and the sequence is alternately well controlled. Furthermore,they have also a characteristic that with the same composition and thesame compositional ratio, they show high fluidity even at a lowtemperature side as compared with the conventional products. Therefore,they are very useful as molding materials for products such as films orfibers. As molding materials, they are particularly suitable forautomobile parts, electrical and electronical parts, thin moldedproducts and precision molded products. They also have a merit that theycan be polymerized at a relatively low temperature in spite of theirhigh heat resistance, since the difference between the solid heatresistance temperature and the sufficiently meltable temperature issmall.

In recent years, there has been a increasing demand for base materialshaving excellent modulus, strength, elongation and heat resistance forall types of products such as fibers, films and molded products.Polyesters have been used widely for molded products of general use.However, many polyesters are poor in the flexural modulus and flexuralstrength and thus unsuitable for applications where a high modulus ofelasticity or high strength is required.

In recent years, an attention has been drawn to liquid crystallinepolyesters as polyesters suitable for applications where a high modulusof elasticity and high strength are required. A particular attention hasbeen drawn to them since W.J. Jackson et al reported on a thermotropicliquid crystalline polymer comprising polyethylene terephthalate andacetoxybenzoic acid in Journal of Polymer Science, Polymer ChemistryEdition, vol 14 (1976), p. 2043, U.S. Pat. Nos. 3,778,410 and 3,804,805,and Japanese Examined Patent Publication No. 18016/1981. In this report,Jackson et al reported that this liquid crystalline polymer exhibitedmodulus of at least 5 times, strength of at least 4 times and impactstrength of at least 25 times as compared with polyethyleneterephthalate, and thus indicated a new possibility for a highperformance resin.

However, this polymer by Jackson et al had a drawback that it was verybrittle and poor in strength and elongation. This is considered to beattributable primarily to the high proportion of a chain of p-oxybenzoicacid residues, as represented by the following formula (13): ##STR3##

Further, the melting point, the softening point, etc. may vary dependingupon the proportion of such chain (13).

On the other hand, many reports are available wherein the moldingconditions have been studied using the polymer of Jackson et al. (Forexample, J.A. Cuculo et al, Journal of Polymer Science, Physical Edition26 179 (1988)).

According to this report, the higher the molding temperature, the higherthe modulus of elasticity, and this is attributable to the fact that anon-melted component exists at a low temperature side, and it givesdefects in the high dimensional structure of the molded product. (Thisindicates that the polymer is in a liquid crystal state only partially.)

This is believed attributable to that the sequence and its distributionas well as the distribution of the composition are widely varied, i.e.non-uniformity is substantial.

This means that high performance of physical properties can not beattained unless the molding temperature is set at a high level relativeto the heat resistance in a solid state. It further indicates that sinceno adequate liquid crystallinity is obtained unless the temperature isat the high temperature side, at the low temperature side i.e. at themelt-initiation temperature or at a temperature slightly higher than themelt-initiation temperature, the fluidity tends to be poor, and moldingof a thin product which is a feature of a liquid crystalline polymer,will be impossible.

The present inventors previously found a copolymer polyester having theelongation at breakage of the polyester developed by Jackson et alimproved (Japanese Unexamined Patent Publication No. 186527/1985). Theconcept was to minimize the proportion of the chain (13) of p-oxybenzoicacid units. Here is the basic idea for reducing the chain (13).

However, according to the method disclosed in Japanese Unexamined PatentPublication No. 186527/1985 or the method of Japanese Unexamined PatentPublication No. 186525/1985, only a random polymer was obtainable inspite of the effort to prevent the chain reaction of p-oxybenzoic acid,and the elongation at breakage was still not high enough and thedifference between the temperature at which the heat resistance in asolid state can be maintained and the temperature at which adequatefluidity is obtainable, was large.

Japanese Unexamined Patent Publication No. 26632/1989 discloses thatwith the liquid crystalline polyester obtained by the method of Jacksonet al, formation of a highly blocked polymer (high proportion of (13))formed by block polymerization of p-oxybenzoic acid is attributable to adeterioration of the physical properties, and it is intended to improvethe physical properties by random polymerization by means of a two steppolymerization method.

However, the polyester obtainable by this method has a high meltviscosity and is poor in the fluidity, and its mechanical propertiessuch as strength and elongation are not good enough, although the heatresistance is high, as confirmed by a duplication test.

This is believed attributable to the fact that p-oxybenzoic acid ispolymerized merely randomly as mentioned above.

Further, in Japanese Unexamined Patent Publication No. 45524/1990, anattempt for improvement has been made by a method of continuously orportionwise adding p-hydroxybenzoic acid and acetic anhydride orp-acetoxybenzoic acid. However, when the ratio of ##STR4## is 80:20(molar ratio), HDT (heat distortion temperature) is as low as 150° C.,and the melt viscosity at 318° C. is 770 poise, and thus the product iseven inferior to that obtained by Japanese Unexamined Patent PublicationNo. 26632/1989. (See Example 1 of Japanese Unexamined Patent PublicationNo. 45524/1990.)

Further, the present inventors previously found a copolymer polyesterwhereby formation of insoluble or infusible particles was controlled(Japanese Unexamined Patent Publication No. 41221/1987). However, thispolyester was sometimes inferior in the heat resistance and unsuitableas an engineering plastic.

U.S. Pat. No. 3,890,256 discloses a polyester having improved abrasionresistance. However, this polyester is produced also in the same manneras in Japanese Examined Patent Publication No. 18016/1981, whereby achain of ##STR5## is likely to form. Therefore, insoluble or infusibleparticles are likely to result, and the elongation at breakage of theresulting polymer tends to be low, and the polymer tends to be brittle.Further, the copolymer component is so high that the heat resistancetends to be inferior.

Further, the above-mentioned U.S. Pat. No. 3,804,805 to Jackson et alincludes an example wherein ##STR6## is employed. However, as confirmedby a duplication test, the product was inferior in the heat resistance,and the mechanical properties were not adequate.

Japanese Unexamined Patent Publications No. 267323/1987, No. 285916/1987and No. 099227/1988 also disclose polymers containing a ##STR7##component. However, the polymers thereby obtained are basically the sameas the polymer obtained by U.S. Pat. No. 3,804,805, and the heatresistance and the mechanical properties are not adequate.

Japanese Unexamined Patent Publication No. 121095/1977 discloses amethod wherein diphenylcarbonate is employed. However, the productobtained by this method is similar to those described above, and theheat resistance and the mechanical properties are not adequate.

Further, Japanese Unexamined Patent Publication No. 17524/1988 proposesa method wherein improvement of the elongation or improvement of theanisotropy of the physical properties is attempted in a system whereinan aliphatic diol or the like other than ethylene glycol is used.However, it does not suggest a method of using ethylene glycol as thesole aliphatic glycol for further improving the above effects(particularly the elongation).

Under these circumstances, the present inventors have conductedextensive researches with an aim to find out a system for a liquidcrystalline polyester comprising constituting units of the followingformulas (1), (2) and (3): ##STR8## whereby the mechanical propertiessuch as the tensile strength, flexural strength and impact strength areimproved, the elongation at breakage is high and the heat resistance isexcellent. While the heat resistance in a solid state is excellent, thepolyester exhibits excellent fluidity once a fluid state is initiated,simply by setting the temperature at a slightly high level (such anexcellent fluidity can be obtained by raising T₁ as far as possible andminimizing T₂ -T₁, where T₁ is a temperature up to which the polyestershows heat resistance in a solid state and T₂ is a temperature at whichit shows excellent fluidity), and thus it is excellent in themoldability and it exhibits high crystallinity in a solid state evenwhen it is a copolymer, whereby it is possible to improve the mechanicalproperties, to improve the resistance against the hydrolysis or tosubstantially improve the mechanical properties or thermal propertieswhen a filler, etc. are incorporated. We consider it possible to obtainsuch a system by controlling the sequence or the compositionaldistribution, more specifically, by adopting a statistically alternatingsequence as described hereinafter. As a result, a method for producing aliquid crystalline polyester having the above-mentioned properties hasbeen found. Further, it has been found that the properties can furtherbe improved by incorporating constituting units of the following formula(5): ##STR9## The present invention has been accomplished on the basisof these discoveries.

According to the first aspect, the present invention provides a liquidcrystalline polyester comprising dicarboxylic acid units of thefollowing formula (1): ##STR10## wherein R¹ is a bivalent aromatichydrocarbon group having from 6 to 18 carbon atoms, diol units of thefollowing formula (2):

    --OCH.sub.2 CH.sub.2 O--                                   (2)

and p-oxybenzoic acid units of the following formula (3): ##STR11##wherein (i) where the moles of said units (1), (2) and (3) arerepresented by [1], [2] and [3], respectively, they satisfy thefollowing formula (I): ##EQU1##

(ii) where among the p-oxybenzoic acid units, (a) p-oxybenzoic acidunits having on their --O-- side a further p-oxybenzoic acid, arerepresented by the underlined portion of the formula (3-1): ##STR12##and (b) p-oxybenzoic acid units having on their ##STR13## side a diolunit of the formula (2), are represented by the underlined portion ofthe formula (3-4): ##STR14## and the moles of (3-1) and (3-4) arerepresented by [3-1] and [3-4], respectively, at least one of r₁ and r₂as defined by the following formulas (II) and (III): ##EQU2## satisfies0≦r₁ ≦0.88, or 0≦r₂ ≦0.88, and

(iii) the viscosity of a solution of the polyester as measured inp-chlorophenol/o-dichlorobenzene (30° C., concentration: 0.5 g/dl) is atleast 0.4 dl/g.

According to the second aspect, the present invention provides a liquidcrystalline polyester comprising dicarboxylic acid units of thefollowing formula (1): ##STR15## wherein R¹ is a bivalent aromatichydrocarbon group having from 6 to 18 carbon atoms, diol units of thefollowing formula (2):

    --OCH.sub.2 CH.sub.2 O--                                   (2)

and oxybenzoic acid units of the following formula (4): ##STR16##wherein (i) where the moles of said units (1), (2) and (4) arerepresented by [1], [2] and [4], respectively, they satisfy thefollowing formula (IV): ##EQU3##

(ii) where among the oxybenzoic acid units, oxybenzoic acid units havingon their ##STR17## side a diol unit of the formula (2), are representedby the underlined portion of the formula (4-1): ##STR18## and the molesof (4-1) are represented by [4-1], r₃ as defined by the followingformula (V): ##EQU4## satisfies 0≦r₃ ≦0.88, and

(iii) the viscosity of a solution of the polyester as measured inp-chlorophenol/o-dichlorobenzene (30° C., concentration: 0.5 g/dl) is atleast 0.4 dl/g.

In the accompanying drawings:

FIG. 1 is a ¹ H-NMR chart used to obtain r₁ in Example 1.

FIG. 2 is a ¹ H-NMR chart after amine decomposition used to obtain r₂ inExample 1.

FIG. 3 is a ¹ H-NMR chart used to obtain r₁ in Example 2.

FIG. 4 is a ¹ H-NMR chart after amine decomposition used to obtain r₂ inExample 2.

FIG. 5 is a graph showing the vibron data of polymers obtained inExample 1 and Comparative Examples 2, 4 and 5, wherein reference numeral1 indicates Example 1, numeral 2 indicates Comparative Example 2,numeral 3 indicates Comparative Example 4, and numeral 4 indicatesComparative Example 5.

FIG. 6 is a graph showing the vibron data of polymers obtained inExample 1, 2, 3 and 4, wherein reference numeral 1 indicates Example 1,numeral 2 indicates Example 2, numeral 3 indicates Example 3, andnumeral 4 indicates Example 4.

FIGS. 7(A) and (B) are DSC charts of polymers obtained in Example 1.FIG. 7(A) shows the data during the temperature drop, and FIG. (B) showsthe data during the temperature rise.

FIGS. 8(A) and (B) are graphs showing X-ray scattering patterns inExample 1. FIG. 8(A) shows the data in a meridional direction, and FIG.8(B) shows the data in an equatorial direction.

FIG. 9 is a ¹ H-NMR chart used to obtain r₁ in Comparative Example 2.

FIG. 10 is a ¹ H-NMR chart used to obtain r₂ in Comparative Example 2.

FIG. 11 is a graph showing the vibron data of the polymers obtained inExamples 9 and 14.

FIG. 12 is a DSC chart (during the temperature rise) of the polymerobtained in Example 14.

FIG. 13 is a ¹ H-NMR chart after amine decomposition used to obtain r₃in Example 9.

FIG. 14 is a ¹ H-NMR chart after amine decomposition used to obtain r₃in Example 12.

Now, the present invention will be described in detail.

The liquid crystalline polyester of the present invention has a featurethat it has high strength and high elongation at breakage, and thus itis a polymer having excellent toughness. Further, among those having thesame composition and the same compositional ratio, it has a feature thatit has excellent heat resistance in a solid state, and theabove-mentioned T₂ -T₁ is very small, whereby it is moldable at a lowtemperature. Besides, it has a feature that it is excellent in themechanical properties when molded at a relatively low temperature i.e.at a temperature slightly higher than the melting point.

Further, such liquid crystalline polyester has a feature that it showshigh crystallinity in a solid state, whereby the resistance againsthydrolytic decomposition is improved, and the mechanical properties andthe thermal properties can be improved when a filler, etc. areincorporated.

Such liquid crystalline polyester has been developed, since the presentinvention has been accomplished on the basis of the following concept.

Namely, in the production of a polymer comprising the followingconstituting units (1), (2) and (3): ##STR19## the desired polymer canbe obtained by minimizing structural units of the formula (13) which isa chain of the units of the formula (3): ##STR20##

In Japanese Unexamined Patent Publications No. 527/1985, No. 26632/1989and No. 45524/1990 directed to improvement of the conventional liquidcrystalline polyester of Jackson et al, the heat resistance and themechanical properties can be improved, but the improvement is merely achange from a statistically blocky structure of the ##STR21## componentin the polymer to a statistically random structure, and the randomnesswas rather qualitative, and the degree of the randomness was notquantitatively analyzed.

The present inventors have found that the above-mentioned physicalproperties can not be fully satisfied by the random structure of theabove component in the polymer, and they can be accomplished for thefirst time by the alternate presence of the component. Namely, theliquid crystalline polyester of the present invention is required tosatisfy at least one of the conditions of 0≦r₁ ≦0.88 and 0≦r₂ ≦0.88,where r₁ and r₂ (sequence forming ratios) are parameters defined by thefollowing formulas (II) and (III), respectively: ##EQU5## Preferably,##EQU6## More preferably, ##EQU7## Still more preferably, ##EQU8## Stillfurther preferably, ##EQU9## The lower limit for r₁ is ##EQU10##Therefore, when [3]=2×[1], it becomes 0. When [3] is larger than this,##EQU11## is proper. However, taking into an error in calculation, etc.into consideration, ##EQU12## is preferred.

The same applies to r₂. Namely, the lower limit of r₂ is ##EQU13##Therefore, when [3]=2×[2], it is 0. However, when [3] is larger thanthis, ##EQU14## is proper. However, taking into an error in calculation,etc. into consideration, ##EQU15## is preferred.

More preferably, r₁ and r₂ are simultaneously in the above mentionedranges.

Now, the meanings of these formulas will be described hereinafter. Theformulas (II) and (III) were led in accordance with the disclosure byB.Vollmert, Polymer Chemistry; Springer-Verlag; NY 1973, p.117-123.

The meanings of the above formulas will now be specifically described.

When the sequence of units of the formula (3) is considered, it isnecessary to distinguish the ether side (--O-- side) from the carbonylside ##STR22## . Namely, on the ether side of the unit (3), twodifferent types of units can be bonded, as shown by a dotted line (. . .) in the following formulas (3-1) and (3-2): ##STR23##

Likewise, on the carbonyl side, two different types of units can bebonded, as shown by the following formulas (3--3) and (3-4): ##STR24##

Here, when the moles of the units corresponding to the underlinedportions of the formulas (3-1), (3-2), (3--3) and (3-4) are representedby [3-1], [3-2], [3--3] and [3-4], respectively,

    [3]≅[3-1]+[3-2]

    [3]≅[3-3]+[3-4]

However, since there may be terminal groups, or the main chain maycontain acid anhydride bonds of the formula: ##STR25## The left handside and the right hand side of the above two formulas i.e.

    {[3]≅[3-1]+[3-2]} and

    {[3]≅[3-3]+[3-4]}

would not necessarily be equal. Namely, [3-2] and [3-4]would notnecessarily be equal.

As a further chain of units, a chain of the formula: ##STR26## isconceivable.

Practically significant are the following two formulas (II) and (VIII):##EQU16## In the analytical method for obtaining r₂ which will bedescribed hereinafter, [3-4] and [3] will be obtained rather than [3-3].

Therefore, assuming [3--3]=[3]-[3-4], the formula (VIII) is representedby the following formula (III) for the sake of convenience: ##EQU17##

The proportions of (1), (2) and (3) will be described hereinafter. Inthe formula (II), values obtained by a NMR method of the polymer wereemployed, and in the formula (III), values obtained by a NMR method ofan amine decomposition product were employed. The proportions of (1),(2) and (3) can also be obtained by a gas chromatography method aftermethanol decomposition, and the results obtained by this method agreedvery well with the results obtained by the NMR method.

Now, the meanings of r₁ and r₂ will be described.

In general, there is a concept called a monomer reactivity ratio for theproduction of a copolymer. Namely, where two monomers M₁ and M₂ arepresent, and the probability for M₁ to enter a position adjacent to theactive species ˜M₁ * is represented by W₁₁ and the concentrations of M₁and M₂ are represented by [M₁ ] and [M₂ ], respectively, the probabilityW₁₁ is represented by the following formula: ##EQU18## where R₁ =k₁₁/k₁₂ ; k₁₁ is a reaction rate constant for M₁ to enter the positionadjacent to ˜M₁ *, and k₁₂ is a reaction rate constant for M₂ to enterthe position adjacent to ˜M₁ *.

Thus, R₁ is a ratio of the reaction rate constants for M₁ and M₂ toenter the position adjacent to ˜M₁ *. In general, W₁₁ may sometimes beobtained by analyzing the polymer. In the case of a chain polymerizationof a vinyl compound, R₁ may sometimes be obtained from the amounts ofthe monomers consumed (or from the proportions of units in the polymer).

On the other hand, in a case like the reaction system of the presentinvention, the reactions are successive, and a side reaction such asester exchange has to be considered. Therefore, the reactivity ratio R₁of the monomers does not Simply determine the composition or thesequence of the polymer.

However, the same concept can be employed. Namely, although thereactivity ratio of the monomers can not be determined, once W₁₁ can bedetermined from the polymer according to the same concept, theformativity ratio of the sequence can be determined therefrom.

Namely, W₁₁ can be replaced by ##EQU19## where [M₁ -M₁ ] is theconcentration of M₁ having M₁ at the adjacent position.

Therefore, the present inventors have adopted r₁ anew and have named itas a sequence formativity ratio. We have defined r₁ by using thefollowing formula which is similar to the above-mentioned formula:##EQU20## i.e. the probability that units of the formula (3) are in theform of (3-1): ##STR27##

When r₁ >1, (3) takes a statistically blocky sequence to (1), where thelarger the value r₁, the higher the blocking nature, i.e. the larger theproportion of [13].

When r₁ ≅1, (3) takes a statistically random sequence to (1). This meansthat the ratio of [13] to [3] in the polymer is the same as theproportion of [3] when [3] and [1] constitute the entire composition.

Further, when r₁ <1, the proportion of [13] tends to be small. Namely,this means that (3) tends to be statistically alternate relative to (1).The smaller the value r₁, the more the alternate sequence. When r₁ =0,there will be no formation of [13].

However, when the proportion of [3] increases to a level of [3]>2×[1],r₁ will be represented substantially by the following formula: ##EQU21##When ##EQU22## the polymer will be an ideal alternating copolymer.

From the opposite aspect, this means that when r₁ >1, the proportion ofthe sequence represented by the formula: ##EQU23## is high.

When r₁ ≅1, the sequence of (14) is a statistically random.

When r₁ <1, the sequence of (14) is less.

Namely, a conventional liquid crystalline polyester having the samecomposition and the same compositional ratio, has a higher proportion ofthe sequence of (14) than the polyester of the present invention.

This is believed attributable to the fact that it has been difficult toreduce the sequence of (14) according to conventional methods.

Now, r₂ will be discussed.

Also with respect to r₂, the formula (III) was prepared, paying anattention to the constituting units on the carbonyl side of the units ofthe formula (3).

Thus, r₂ is defined by the formula (III): ##EQU24## represents the ratioof ([3]-[3-4]) to [3], i.e. the probability that units of the formula(3) ##STR28## are in the form other than ##STR29## In this case, forexample, ##STR30## is taken as containing two units of the formulacorresponding to the underlined portion of the formula (3-4): ##STR31##

Namely, they are two units as identified by the two underlines in thefollowing formula: ##STR32##

When r₂ >1, (3) takes a statistically blocky sequence to (2).

When r₂ ≅1, (3) takes a statistically random sequence to (2).

Further, when r₂ <1, (3) takes a statistically alternate sequence to(2).

Further, in a case of a polymer comprising four constituting unitsincluding a small amount of a kink component of the formula (5):##STR33## parameter r₃ (sequence formativity ratio) defined by thefollowing formula (V): ##EQU25## is required to satisfy a conditionrepresented by the following formula:

    0≦r.sub.3 ≦0.88

preferably ##EQU26## more preferably, ##EQU27## a still more preferably,##EQU28## most preferably, ##EQU29## As mentioned above, however, when[4]>2×[2], ##EQU30## is proper. However, taking an error in calculationinto consideration, it is preferred to employ the following formula:##EQU31##

In the same manner as in the case of r₂,the meanings of the aboveformulas will be specifically described as follows. With respect to thesequence of the oxybenzoic acid unit of the formula (4), two differenttypes of units can be bonded on its carbonyl side as indicated by dottedline (. . . ) in the following formulas (4-3) and (4--4). ##STR34##

Here, when the moles of the units corresponding to the underlinedportion in the formulas (4-3) and (4--4) are represented by [4-3] and[4--4], respectively,

    [4]≅[4-3]+[4--4]

    ([4]=[3]+[5]).

A practically meaningful formula is as follows: ##EQU32## However, bythe analytical method for obtaining r₃, which will be describedhereinafter, [4--4] and [4] are obtainable rather than [4-3]. Therefore,assuming [4-3]=[4--4], the formula (IX) is represented by the formula(V) for convenience sake: ##EQU33##

In this case, the calculation should be made based on the proportion ofthe constituting unit of the formula (3--3): ##STR35## However, by theanalytical methods presently available, the unit of the formula (3--3)can not be distinguished from the following units: ##STR36## Further,since the unit of the formula (5) is in a small amount as compared withthe unit of the formula (3), the proportions of (3-5), (3-6) and (3-7)are substantially small as compared with (3--3). ##STR37##

Therefore, on an assumption that the small proportion of (4-3)corresponds to a small proportion of (3--3), r₃ was calculated in thesame manner as r₂.

In the case of the liquid crystalline polyester of Jackson et al, (3)takes a block structure to (1). This has been proved by V.A. Nicely etal of the same Eastment group (Macromolecules, 20, 573, (1987)). Nicelyet al use the following formula: ##EQU34## and determine whether or notthe product has a block structure on the basis of whether m is largerthan 1. This is based on an idea that judgment be made on the basis ofwhether the proportion of [3-1] is larger or smaller than the proportionof [3] when [3] and [1] constitute the entire composition. The method bythe present inventors is believed to be better than this method as astandard for judgment. In any case, it has been already proved that thepolymer of Jackson et al has a block structure since m=1.3. (However,their measurement is restricted within a range of ##EQU35## Whereas, thepresent inventors have measured also within a range of ##EQU36## thistime, which as proved again that the polymer has a block structure.)

Those disclosed in Japanese Unexamined Patent Publications No.186527/1985, No. 26632/1989 and No. 45524/1990 have also randomstructures.

However, it can not be denied that there has been an alternating systemknown for a polyester of a composition similar to the present invention.For example, R.W. Lenz et al have prepared a polyester of alternatingsystem using a compound of the formula (6-1) and ##STR38## by aninterfacial method (a solution method) (Polymer Journal 14 (1) 9(1982)). However, η_(inh) is as low as 0.178, whereby the mechanicalproperties desired for a polyester can not be expected. (British PolymerJournal 12 (4) 132 (1980) presents an article by the same authors, andalthough there is no disclosure of η_(inh), from other data, the productis considered to be the same as disclosed in the above-mentioned PolymerJournal.)

Further, there has been a report on a study as to the difference in meltbetween a completely alternating system and a non-alternating systemwith respect to a compositional system other than the present invention(S.I. Stupp et al, Macromolecules 21 1228 (1988)). It is certainly truethat in an alternating system, the range for transformation from solidto liquid crystal is narrow. However, for the alternating system in thisarticle, monomers have to be sequentially synthesized, and the synthesisof the monomers is not easy. Besides, no mechanical properties of theproduct has been examined.

The liquid crystalline polyester of the present invention wherein atleast one of r₁, r₂ and r₃ as defined above is less than 0.88, has, forexample, the following characteristics.

1. It has high tensile strength and flexural strength.

2. It has high impact strength.

3. It has high elongation at breakage.

4. With the same composition and the same compositional ratio, the heatresistance is high.

5. Since T₂ -T₁ is small, it is possible to lower the moldingtemperature.

6. A product molded at a lower temperature has better mechanicalproperties.

7. The apparent activating energy of the melt viscosity is small.

8. The crystallinity is high.

9. The resistance against hydrolytic decomposition is excellent.

10. The effects of incorporation of fillers, etc. are distinct.

Further, the physical properties of the polymer of the present inventionare far superior in the balance of the mechanical properties and thethermal properties to the conventional products, although it may beinferior in certain individual physical properties. Further, the factthat the molding temperature can be lowered in spite of the high heatresistance, means that the polymerization temperature for its productioncan be lowered, and it is possible to produce a polymer having excellentheat resistance by a conventional apparatus.

R¹ in the dicarboxylic acid units of the formula (1) is a bivalentaromatic hydrocarbon group having from 6 to 18 carbon atoms.Specifically, it includes, for example, ##STR39## (wherein --X--includes, for example, --O--, --S--, --SO₂ --, --CH₂ -- and --C(CH₂)₂--). These aromatic hydrocarbon groups may be used alone or incombination as a mixture to form a copolymer. Among them, ##STR40## arepreferred. When used alone, ##STR41## is preferred. Particularlypreferred is ##STR42## When used in combination as a mixture, at leastone of the units is preferably selected from ##STR43## and a total ofsuch units preferably constitutes at least 50 mol %, more preferably atleast 66 mol %.

As a preferred mixed system, a combination of ##STR44## may bementioned. These groups may be used in a combination of three or moredifferent types, but it is preferred to use up to two different types.

In the present invention, the ratio of the moles [1] and [3] of theunits of the above formulas (1) and (3) is required to satisfy thefollowing formula from the viewpoint of production: ##EQU37## Namely, inthe process of the present invention, ##STR45## are required, and when##STR46## is not added thereto, the ratio will necessarily be: ##EQU38##

The liquid crystalline polyester of the present invention can, ofcourse, be produced by a method other than the method of the presentinvention. Even in such a case, however, it is necessary to satisfy##EQU39## Namely, if ##EQU40## the heat resistance tends to be low, suchbeing undesirable. From the viewpoint of heat resistance, ##EQU41## ispreferred, and ##EQU42## is more preferred. When ##STR47## is used for(1), ##EQU43## is particularly preferred. On the other hand, the upperlimit is ##EQU44## If the ratio exceeds this upper limit, the absolutevalue of the chain of p-oxybenzoic acid units tends to be large, suchbeing undesirable. Within this condition, ##EQU45## is preferred, and##EQU46## is particularly preferred. The ratio of [1] to [2] is usually##EQU47## preferably ##EQU48## more preferably ##EQU49## with a view toincreasing the degree of polymerization.

In order to improve the resistance against hydrolytic decomposition,##EQU50## is further preferred. When the terminal groups are to besealed, ##EQU51## is preferred, to the contrary.

When ##STR48## is used, the molar ratio is usually ##EQU52## preferably##EQU53## more preferably ##EQU54## most preferably ##EQU55##

Then, with respect to ##EQU56## is preferred, ##EQU57## is morepreferred, and ##EQU58## is particularly preferred.

From the viewpoint of the heat resistance and crystallinity, the smallerthe [5], the better. If ##EQU59## the strength and elongation are not upand the heat resistance tends to be substantially low, such beingundesirable. From the viewpoint of the strength or elongation, thelarger the [5], the better. Therefore, the amount of [5] should bedetermined from the balance between the mechanical properties and thethermal properties. In any case, the product of the present invention isbetter in such a balance than the conventional products of ComparativeExamples.

The polyester of the present invention does not substantially containunits of the formula (15) which is disclosed in Japanese UnexaminedPatent Publication No. 186527/1985: ##STR49## If it contains such units,the heat resistance tends to be substantially low, such beingundesirable. Further, the crystallinity also tends to be low. However,if units of the formula (15) are present, the moles of (15) shall not beincluded in the moles of [3].

Now, the measuring method for the units of (1), (2), (3), (3-1), (3-2),(3-4), (4) and (4-4) and the calculation for r₁, r₂ and r₃ will bedescribed.

Firstly, with respect to r₁, the calculation is basically the same asthe method of Nicely et al mentioned above.

Namely, r₁ was obtained by means of ¹ H-NMR. For NMR, AM-500manufactured by BRUKER was used, and trifluoroacetic acid or a solventmixture of trifluoroacetic acid and pentafluorophenol, was used as thesolvent. The measurement was conducted at room temperature in the caseof the system using trifluoroacetic acid alone and at 60° C. in the caseof the solvent mixture system of trifluoroacetic acid andpentafluorophenol. From each ¹ H-NMR spectrum, the signal intensity ofeach of the signal (H₂ : 7.55 ppm) derived from (3-1): ##STR50## and thesignal (H_(b) about 7.45 ppm) derived from the chain (3-2) of thedicarboxylic acid unit (1) and the p-oxybenzoic acid unit (3): ##STR51##was obtained, and further from the signals at about 8.3 ppm and about8.5 ppm, the ratio of (1) to (3) was obtained, and r₁ was calculatedtherefrom. According to this method, it is possible to obtaininformation of the sequence on the --O-- side of the compound of theformula (3).

Now, with respect to the method for determining r₂ and r₃, these valuescould not be obtained from NMR of the polymer. Under the circumstances,the present inventors have conducted an extensive study and have found amethod for obtaining r₂ and r₃. Namely, it has surprisingly be foundthat when the liquid crystalline polyester of the system of the presentinvention is reacted with a primary amine, the ester bonds of theformula (4--4) such as ##STR52## remain selectively without beingcleaved, while other ester bonds (such as ester bonds of e.g. (3--3) and(3-2) and (14)) are cleaved. By utilizing this, it is possible toanalyze the sequence of the liquid crystalline polyester of the systemof the present invention. More specifically, this method comprisespulverizing e.g. the liquid crystalline polyester of the system of thepresent invention, treating the pulverized sample with a large excessamount of n-propylamine at 40° C. for 90 minutes, and thenquantitatively analyzing the decomposition product thereby obtained bythe same 500 MHz ¹ H-NMR as described above. The ¹ H-NMR measurement isconducted by using deuterated methanol, a solvent mixture of deuteratedDMSO and deuterated methanol, or deuterated trifluoroacetic acid, as thesolvent, to quantitatively analyze (3-4) and (4--4). The proportions of(2), (3) and (5) were calculated by using the respectively identifiedpeak intensities. According to this method, information on the sequenceon the ##STR53## side of the units (3) and (4) will be obtained. Basedon such information, r₂ and r₃ were calculated.

The proportion of (1), (2), (3) or (5) was measured by further enlargingFIG. 1, FIG. 2 or FIG. 11. As an error, when ##EQU60##

From the foregoing discussion, r₁ and r₂ or r₃ may appear to be thesame. However, there is a substantial difference from the viewpoint ofthe above described analytical methods. Namely, (3-1) and (3-2) can bedistinguished by ¹ H-NMR, and r₁ can therefore be expressed by means of[3-1]. However, by the amine decomposition method, (3) and (3-4) aredistinguished rather than (3--3) and (3-4). Accordingly, r₂ isaccurately expressed by means of [3]-[3-4]. Because of terminal groups,etc., [3-1] and {[3]-[3-4]} are not necessarily equal. Also from theviewpoint of precision in measurement, they may not necessarily beequal. The same as to r₂ applies to r₃ As described in the foregoing,the proportion of (1), (2) or (3), or (1), (2), (3) or (5) was obtainedalso by gas chromatography after methanol decomposition. The data agreedvery well to the data obtained by the NMR method.

Such a more alternating polyester is considered to be uniform not onlywith respect to the sequence but also with respect to the compositionaldistribution. For example, according to the vibron data shown in FIGS. 5and 6, it is evident that only the polyester of the present inventionsatisfies 0≦a≦80° C. where a=T₂ -T₁ where T₁ is the temperature at whichE'=3×10¹⁰ dyne/cm² as an index for heat resistance (E' is storagemodulus) and T₂ is the temperature at which E'=5×10⁹ dyne/cm² as theminimum temperature for sufficient fluidity. Preferably 0≦a≦75° C., morepreferably 0≦a≦70° C., still more preferably 0≦a≦65° C., and mostpreferably 0≦a≦60° C. When a m-substituted component as the kinkcomponent is contained, 0≦a≦90° C., preferably 0≦a≦85° C., morepreferably 0≦a≦80° C. The smaller the value a, the lower the temperaturefor fluidity in spite of high heat resistance in a solid state.

In a case where the constituting units are solely (1), (2) and (3) andR¹ is ##STR54## is satisfied (provided ##EQU61## Therefore, T₁ can becontrolled by the compositional ratio.

From the viewpoint of the mechanism properties, when R¹ in the units (1)is ##STR55## and ##EQU62## the liquid crystalline polyester of thepresent invention shows an improvement in the elongation at breakage byat least about 20% and an improvement in the strength by from about 10to 20% as compared with conventional liquid crystalline polyesters. Asmentioned above, according to the present invention, a (T₂ -T₁) issmall. This means that the polymer has heat resistance and can be moldedat a low temperature, and at that time, the melt viscosity is very low,since it is melted in its entirety. This corresponds to the fact thatthe sequence is statistically alternating i.e. the values of r₁, r₂ andr₃ are small.

By tracing the change of the structure due to the temperature change bya small angle X-ray scattering method, it can be confirmed that nostructure (particularly no high dimensional structure) remains afterbeing melted. (Further, the change in the crystal structure can beascertained by a wide angle X-ray scattering method as describedhereinafter.)

As the sequence becomes more alternating i.e. more uniform, it can beexpected that with the same compositional ratio, the crystallinity willbe improved. This can be confirmed by measuring the crystallinity by DSCor X-ray scattering.

It is possible to ascertain the presence or absence of crystals or tocompare the sizes or types of crystals, by ΔH at Tc by DSC, or by thepeak intensities or the value at 2θ by X-ray. Especially in the case ofthe same compositional ratio, when molding is conducted under the samemolding conditions, if there is a difference in the primary structure,particularly in the sequence, such a difference can be ascertained bytwo types of analyses. For example, if a rod is prepared and its wideangle X-rays are measured to study the scattering patterns in theequatorial direction and in the meridional direction, it becomesapparent that as compared with the conventional polymers having the samecomposition and the same compositional ratio, the polymer of the presentinvention has features that the size of the crystal lattice is small,and the distance between crystal molecules is small.

The solution viscosity η_(inh) of the liquid crystalline polyesterobtained by the present invention can be determined as follows.

Using p-chlorophenol/o-dichlorobenzene=1/1 (weight ratio) as thesolvent, a sample is dissolved therein at room temperature to obtain asolution having a concentration of 0.5 g/dl, and the measurement isconducted at 30° C. The solution viscosity is obtained by the followingformula. ##EQU63## t₀ : Falling velocity (sec) in the blank (the solventonly) t: Falling velocity (sec) in the solution at a concentration of0.5 g/dl

The polyester of the present invention has a characteristic that withthe same composition and the same compositional ratio, the meltviscosity is small and the fluidity is improved relative to the degreeof polymerization (the solution viscosity may be used as an index of thepolymerization degree). If this solution viscosity η_(inh) is less than0.4 dl/g, the mechanical properties tend to be poor, such beingundesirable. Preferably η_(inh) ≧0.5, more preferably η_(inh) ≧0.6, mostpreferably η_(inh) ≧0.7. Further, with the liquid Crystalline polyesterof the present invention, the solution viscosity can be measured by thismethod, i.e. it can be dissolved substantially completely. This alsoindicates that there exists no long chain polymer of (3). Further, thisindicates also that the compositional distribution is uniform.

The liquid polyester obtained by the present invention can be dissolvedin phenol/1,1,2,2-tetrachloroethane=1/1 (weight ratio) or inhexafluoroisopropanol. This indicates that the composition is uniform,and there exists no substantial long chain of (3).

Now, the method for its production will be described.

The production of a polyester which satisfies at least one of 0≦r₁≦0.88, 0≦r₂ ≦0.88 and 0≦r₃ 0.88 can not be attained by conventionalmethods such as those disclosed in Japanese Examined Patent PublicationNo. 18016/1981 and Japanese Unexamined Patent Publications No.87125/1983, No. 186525/1985, No. 26632/1989 and No. 45524/1990.

As a method for producing a polyester wherein r₁, r₂ and r₃ satisfy theabove ranges, the present inventors have considered that in order toprevent formation of a chain of (3), it is advisable to let the units of##STR56## be apart from one another from the stage of startingmaterials, i.e. to use e.g. ##STR57## and/or ##STR58## and/or ##STR59##

Namely, when the diol component is

    --OCH.sub.2 CH.sub.2 O--                                   (2),

as in the present invention, it has commonly been considered that undera high temperature condition ester exchange or acidolysis occursactively, whereby units of (3) will form a block or random structure.However, it has been unexpectedly found that the component (2) hardlyundergoes ester exchange. Namely, with the polymer produced by themethod of Jackson et al, the above component (14) remains, and thereforethe proportion of the chain of (3) increases. The above-mentioned othermethods were designed to let ester exchange or acidolysis occur as faras possible.

Whereas, the present invention is based on an idea of utilizing thephenomenon that the ester exchange of the --OCH₂ CH₂ -- componentunexpectedly hardly takes place at a high temperature condition.

The method of the present invention will be described in further detail.

Namely, the method comprises adding ##STR60## and/or ##STR61## and##STR62## then, if necessary, adding ##STR63## and/or ##STR64## then, ifnecessary, adding acetic anhydride, and in some cases, (if necessary)further adding ##STR65## and/or ##STR66## and in some cases, (ifnecessary) further adding ##STR67## and/or ##STR68## followed by e.g.acetylation at a temperature of from 100° to 170° C. This acetylation isconducted for from 5 minutes to 3 hours, preferably from 20 minutes to1.5 hours. Acetic anhydride is used preferably in an amount of from thesame amount to 1.5 times the amount of the hydroxyl groups in thestarting materials. Namely, if the acetic anhydride is represented by(16), and the moles of (6), (9) and (16) are represented by [6], [9] and[16], ##EQU64## is preferred, and ##EQU65## is particularly preferred.

Even in a case where starting materials containing no hydroxyl groupsare used, a small amount of acetic anhydride may be employed,.sincethere is a merit that the polymerization rate can thereby be increased.The reaction may be conducted in the absence of a catalyst. Otherwise, acatalyst may be added as the case requires.

Then, the temperature is raised to conduct polymerization. Thepolymerization is conducted at a temperature of from 220° to 340° C. Itis particularly preferred to conduct the polymerization at a temperatureof from 260° to 320° C. More preferably, the polymerization is conductedat a temperature of from 265° to 300° C., most preferably from 265° to280° C. There is a merit that the polymerization can be conducted at alow temperature in spite of the heat resistance in a solid state.Further, the time required for gradually reducing the pressure from 760mmHg to 1 mmHg is usually at least 30 minutes, preferably at least 60minutes. It is particularly important to conduct the reduction of thepressure from 30 mmHg to 1 mmHg gradually.

The polymerization can be conducted in the absence of a catalyst, but itis usually conducted in the presence of a catalyst as the case requires.As the catalyst to be used, an ester exchange catalyst, apolycondensation catalyst, an acylation catalyst or a decarboxylic acidcatalyst, may be employed. These catalysts may be used in combination asa mixture. Preferred catalysts include, for example, Ti(OBu), BuSnOOH,Sn(OAc)₂, Sb₂ O₃, Fe(acac)₃, Zn(OAc)₂, Co(OAc)₂, NaOAc and KOAc. Thecatalyst is used usually in an amount of from 5 to 50,000 ppm,preferably from 50 to 5,000 ppm, relative to the polymer.

The polymerization time may be within 10 hours. It is particularlypreferred to conduct the polymerization within 7 hours. Most preferably,it is conducted within a range of from 1 to 4 hours.

As mentioned above, there is a merit in that this polymerization can beconducted at a low temperature. There is a further merit that even at alow temperature, the product can be easily withdrawn without anytrouble. This is also considered attributable to the fact that thesequence is well controlled.

The feeding ratio of ##STR69## and/or ##STR70## and ##STR71## ispreferably ##EQU66## more preferably ##EQU67## Likewise, the feedingratio of ##STR72## and/or ##STR73## and/or ##STR74## and/or ##STR75## isusually ##EQU68## preferably ##EQU69## If the above value exceeds 0.3,the heat resistance tends to be low, and the crystallinity tends todeteriorate, whereby the fluidity tends to be poor, such beingundesirable.

It is preferred to use ##STR76## and ##STR77## rather than ##STR78## and##STR79## for improving the physical properties and increasing the rateof polymerization.

The ratio of [9] and [10] is usually ##EQU70## preferably ##EQU71## morepreferably ##EQU72##

Now, a method wherein a compound of the following formula (11) is used,will be described.

Acetic anhydride is added to ##STR80## and a compound of the formula (9)and/or a compound of the formula (10): ##STR81## as the startingmaterials, followed by acetylation at a temperature of from 100° to 170°C. This acetylation is conducted for from 5 minutes to 3 hours,preferably from 20 minutes to 1.5 hours. Acetic anhydride is usedusually in amount of ##EQU73##

The compounds (11), (8), (9) and (10) may preliminarily be reacted priorto the acetylation. Otherwise, the compounds (11), (9) and (10) maypreliminarily be reacted prior to the acetylation. In such a case, themolar ratio is preferably within a range of ##EQU74## more preferably##EQU75##

A solvent may be used for this reaction. However, it is preferred toconduct the reaction in the absence of a solvent to avoid the necessityof a subsequence step of removing it. To conduct the reaction of (11)and (9) and/or (8), it is advisable to add (9) and/or (8) into a melt of(11). However, if the temperature is too high, a ##STR82## structuretends to be formed by (11) and (9), such being undesirable. Therefore,the temperature is preferably from 145° to 220° C., more preferably from170° to 210° C. In the case of (11) and (10) and/or (8), a ##STR83##structure is scarcely formed, and the temperature may be slightly high.However, if the temperature is too high, a structure of (13) tends to beformed at the initial state of the reaction, such being undesirable.Specifically, it is preferred to conduct this reaction at a temperatureof from 145° to 230° C.

From the viewpoint of the polymerization degree, the ratio of (11) and(8) is preferably ##EQU76## more preferably ##EQU77##

With respect to the overall feeding ratio, the ratio of (11) and (9),(10) is usually ##EQU78## preferably ##EQU79##

Now, the ratio of (9-1), (9-2), (10-1) and (10-2) as the constitutingcomponents of (9) and (10), is preferably ##EQU80## more preferably##EQU81## most preferably ##EQU82## If ##EQU83## the heat resistancetends to be low, and the liquid crystallinity also tends to be low,whereby the fluidity tends to deteriorate.

The whole or part of (8) and the whole or part of (10) may be addedduring the acetylation or after the acetylation. After completion of theacetylation, the temperature is raised to initiate the polymerization.The polymerization is conducted at a temperature of from 220° to 340°C., preferably from 260° to 320° C., more preferably from 265° to 300°C. Particularly preferred is from 265° to 290° C., and most preferred isfrom 265° to 280° C. If the temperature is lower than 260° C., thepolymerization speed tends to be slow. On the other hand, if it exceeds320° C., the physical properties of the resulting polymer tend to bepoor. As to the catalyst, the same as described with respect to theabove-mentioned method will apply. This method has a merit that pipings,etc. will not be soiled since sublimation is little.

The difference between the method of the present invention and themethod disclosed in Japanese Unexamined Patent Publication No.317524/1988 is that as mentioned above, the inventors of JapaneseUnexamined Patent Publication No. 317524/1988 did not consider itpossible to improve the physical properties when the aliphatic glycolwas ethylene glycol only, and they stated that ester exchange oracidolysis of C₃ or higher was difficult, and they have overcome thisdifficulty. Further, referring to the earlier application (JapaneseUnexamined Patent Publication No. 186525/1985) by the present inventors,they considered it possible to conduct acidolysis sufficiently by usingethylene glycol in this method, and therefore they did not intend toimprove the physical properties by ethylene glycol only, from the verybeginning.

As mentioned above, the present inventors have considered that esterexchange or acidolysis is not sufficient even in the case of ethyleneglycol, and therefore it is advisable to minimize the chain of ##STR84##from the very beginning of the production. This is basically differentfrom the way of thinking by the inventors of Japanese Unexamined PatentPublication No. 317524/1988 such that in the case of ethylene glycol,ester exchange or acidolysis would take place sufficiently.

Further, the liquid crystalline polyester of the present inventionexhibits an optical anisotropy in a molten phase. Especially, whenmelting starts, solid will substantially disappear simply by raising thetemperature slightly from the melt-initiation temperature, andsubstantially all will take a liquid crystalline state. Therefore, thepolyester of the present invention has a feature that it is far superiorto conventional polyesters in the fluidity as represented by η_(inh).Therefore, the moldability is good, and a usual melt-molding such asextrusion molding, injection molding or compression molding can beapplied to form it into molded products, films, fibers, etc.

With respect to the melt viscosity, the polyester of the presentinvention shows liquid crystallinity, whereby the melt viscosity isgenerally low. For example, the melt viscosity at 275° C. under 10³sec⁻¹ is not more than 5000 poise, preferably from 30 to 3000 poise,more preferably from 100 to 2500 poise. Further, in polyester with thesame composition and same compositional ratio, with the same η_(inh),the product of the present invention will have the lowest melt viscosityat 275° C. Further, it is a feature of the product of the presentinvention that the ratio of the melt viscosity at 275° C. to the meltviscosity at 290° C. is small. It is also a feature of the product ofthe present invention that the ratio of the melt viscosity at atemperature higher by from 8° to 18° C. than T_(m) to the melt viscosityat a temperature higher by from 23° to 33° C. than T_(m) is small.

The polyester of the present invention has high fluidity and istherefore particularly suitable for e.g. precision molded products. Forexample, it can be used for automobile parts, parts of informationmaterials such as compact discs or flexible discs, or parts ofelectronic materials such as connectors, IC sockets, etc.

Further, at the time of molding, fibers such as glass fibers or carbonfibers, fillers such as talc, mica or calcium carbonate, a nucleatingagent, a pigment, an antioxidant, a lubricant, or other packingmaterials or additives such as a stabilizer or a flame retardant, or athermoplastic resin, may be added to the copolymer polyester of thepresent invention to impart a desired property to the molded product.

Furthermore, the copolymer polyester of the present invention may beblended with other polymer or may be alloyed with other polymer toobtain a composition having the merits of the two polymers.

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to such specific Examples.

In the Examples, the melt viscosity was measured by means of a flowtester manufactured by Shimadzu Corporation using a shear rate (γ) of1000 sec⁻¹ and a cylinder nozzle length/diameter=20.

The optical anisotropy (liquid crystallinity) was observed by means of apolarizing microscope provided with a hot stage.

Molding was conducted by a 0.1 oz injection molding machine manufacturedby The Japan Steel Works, Ltd., and molded specimens were prepared bymeans of molds A and B. Further, by a 0.3 oz injection molding machinemanufactured by Sumitomo Heavy Industries, Ltd., molded specimens wereprepared by means of mold C.

HDT (heat distortion temperature) is a value obtained by taking vibrondata from the molded specimens prepared by the 0.1 oz injection moldingmachine, while HDT is obtained from molded specimens prepared by a 2.5oz injection molding machine manufactured by Toshiba Kikai from a liquidcrystalline polyester developed by us or from a commercial product ofliquid crystalline polyester, and utilizing the interrelation betweenthe two.

As the vibron, reovibron manufactured by Toyo Baldwin Co. was used, andmolded specimens obtained by means of mold A of the above 0.1 ozinjection molding machine was used under 110 Hz.

The Vicat softening temperature was measured by an automatic HDTmeasuring apparatus manufactured by Toyo Seiki, using as a sample amolded specimen prepared by the above-mentioned 0.1 oz injection moldingmachine, at a heating rate of 50° C./hr, whereby the temperature atwhich the needle penetrated in a depth of 1 mm was taken as thesoftening temperature.

Tensile properties (tensile modulus, tensile strength and elongation atbreakage) were measured by means of TENSILON/UTM-IIIL manufactured byToyo Baldwin Co., with respect to the molded specimens prepared by meansof molds A and B of the above 0.1 oz injection molding machine and withrespect to the molded specimens prepared by means of mold C of the 0.3oz injection molding machine.

DSC was measured by means of TA2000 manufactured by Du Pont. As thesample, a powder was used, and it was heated to 350° C. at a rate of 20°C./min, then left to stand for 5 minutes and then cooled to 20° C. at arate of 20° C./min. Then, it was left to stand for 5 minutes and thenheated to 350° C. at a rate of 20° C./min. The charts of the coolingstep and the second heating step are shown in FIGS. 7(A) and 7(B).

The X-ray scattering was measured by means of X-ray generating apparatusRAD-B system (maximum output: 12 kW) manufactured by Rigaku Denki K.K.As the sample table, a fiber sample table manufactured by the samecompany was used. A sample was extruded from a nozzle of 1 φ at 275° C.or 290° C. and molded into a rod shape of 0.37 φ, which was furthersubjected to heat treatment at 130° C. for 12 hours before use. By thismolding, the sample was highly oriented in the direction of extrusion.

With respect to the elongation at breakage as a tensile property, themolded specimens (dumbbell specimens) prepared by the 0.1 oz injectionmolding machine (mold A, B) and by the 0.3 oz injection molding machine(mold C) usually have low elongation as compared with the moldedspecimens according to ASTM. Likewise, the molded specimens prepared bymeans of mold A of the 0.1 oz injection molding machine usually shows asubstantially low strength as compared with the molded specimensaccording to ASTM. Accordingly, if an elongation is at least 3.5% withsuch molded specimens, such polymer can be regarded as fairly tough.Likewise, if it is less than 3.0%, such polymer can be regarded asbrittle.

Izod impact strength was measured in accordance with ASTM D-256(notched).

REFERENCE EXAMPLE 1

Preparation of ##STR85##

Into xylene, p-hydroxybenzoic acid and ethylene glycol were charged tobring the molar ratio of p-hydroxybenzoic acid/ethylene glycol=2/1, andp-toluenesulfonic acid was charged as a catalyst. The mixture was heatedto the reflux temperature of xylene and reacted.

After completion of the reaction, unreacted materials were removed bywashing with water to obtain ##STR86## in high purity. The structure wasconfirmed by ¹ H-NMR.

REFERENCE EXAMPLE 2

Preparation of ##STR87##

Into an autoclave, 138 parts by weight of p-hydroxybenzoic acid, 1 partby weight of Na₂ CO₂ and 300 parts by weight of isopropanol werecharged, and at 90° C., 66 parts by weight of ethylene oxide was addedthereto, and the reaction was conducted. After the reaction, the mixturewas cooled, and the precipitate was collected by filtration andrecrystallized twice from water to obtain 55 parts by weight ofp-hydroxylbenzoic acid-β-hydroxyethyl ester ##STR88## having a meltingpoint of 141° C. The structure was confirmed by ¹ H-NMR.

REFERENCE EXAMPLE 3

Preparation of ##STR89##

The compound was prepared in accordance with the method disclosed inKobunshi Kagaku (Polymer Chemistry) 30, 572 (1973). Namely, it wasprepared by an ester exchange reaction of m-oxybenzoic acid methyl esterand ethylene glycol, and its structure was confirmed by ¹ H-NMR.

EXAMPLE 1

Into a glass tube equipped with a stirrer, a nitrogen inlet and a vacuumport, 48.6 g (0.161 mol) of ##STR90## 26.7 g (0.161 mol) of ##STR91##and 44.4 g (0.322 mol) of ##STR92## were charged, and the glass tube wasflushed with nitrogen under vacuum. Then, 82.1 g (0.81 mol) of aceticanhydride was added thereto, and the system was heated to 140° C. understirring and maintained at 140° C. for one hour. Then, the system washeated to 275° C. over a period of 1.5 hours. When the temperaturereached 275° C., vacuuming was started. It was initially planed toreduce the pressure to 10 mmHg in one hour and then from 10 mmHg to 1mmHg over a period of 1.5 hours. However, when the pressure was reducedto 6 mmHg after one hour and 55 minutes from the initiation of thevacuuming, the torque was sufficiently high, and therefore thepolymerization was terminated.

Then, the system was left to stand still, and the pressure was returnedto a normal level. Then, the formed polymer was discharged from thebottom of the glass tube. The dischargeability was excellent.

The polymer was formed into chips and dried under vacuum at 120° C.overnight. This polymer had η_(inh) of 0.98, and the melt viscosity wasas shown in Table 1.

With this polymer, r₁ =0.75, and r₂ =0.78. FIG. 1 shows a NMR chart usedfor obtaining r₁ =0.75, and FIG. 2 shows a NMR chart after aminedecomposition used for obtaining r₂ =0.78. Further, various mechanicalproperties were as shown in Table 1.

Further, FIG. 5 shows various vibron charts including Example 1 of thepresent invention. The one shown in the Figure, is the chart of Example1.

Vibron T₁ is very high at a level of 224° C. which is higher by about20° C. than the conventional polymers having the same composition andthe same compositional ratio (Comparative Examples 2, 4, 5 and 6), andT₂ was 270° C. and lower than the conventional polymers of the samecomposition and the same compositional ratio except for ComparativeExample 4.

T₂ -T₁ of this polymer was 46° C. which is a width substantially smallas compared with conventional polymers.

Among the mechanical properties, especially with respect to theelongation at breakage, the polymer of the present invention shows avalue of 3.7% whereas the conventional polymers (Comparative Examples 2,4, 5 and 6 given hereinafter) show values not higher than 3%. Namely,this indicates that the polymer of the present invention has substantialtoughness, while those having values not higher than 3% are ratherbrittle. Further, as compared with the Comparative Examples, the meltviscosity is low relative to η_(inh). Further, the product of thepresent invention shows better mechanical properties as the moldingtemperature is lower, while the conventional polymers (ComparativeExamples 2 and 4) show better mechanical properties as the moldingtemperature is higher.

FIG. 7 shows a DSC chart of the polymer obtained in Example 1. Thecrystallinity is very high (the value ΔH is large) and T_(m) =265.7° C.,which very well corresponds to T₂ =270° C.

FIG. 8 shows the results of the X-ray scattering measurement. Namely,the positions of peaks of the scattering pattern in the meridionaldirection are as follows:

    ______________________________________                                        Meridional direction                                                                          Positions of peaks                                            ______________________________________                                        15.2°    --                                                            23.5°    very weak                                                     28.05°                                                                 35.9°    very week                                                     39.4°    very weak                                                     43.65°                                                                 ______________________________________                                    

The positions of peaks of the scattering pattern in the equatorialdirection are as follows:

    ______________________________________                                        Equatorial direction                                                                          Positions of peaks                                            ______________________________________                                        20.4°                                                                  35.8°                                                                  ______________________________________                                    

Also from these results, it is evident that the scattering intensity ishigh, and the crystallinity is high. The peak observed in the scatteringpattern in the meridional direction, such as the peak at 15.2° , is at awide angle side than the peak of the conventional polymer with the samecompositional ratio. Likewise, the position of the peak observed in thescattering pattern in the equatorial direction is 20.4° , and thus thescattering angle is larger than the conventional polymer. Namely, thisindicates that the size of the crystal lattice in the direction of thefiber axis (i.e. the fiber period) is smaller than the conventionalpolymers. Also with respect to the packing between molecules, thedistance between molecules is shorter than the conventional polymers,and the packing of molecules is denser.

Using this sample, the lzod impact strength was measured and was foundto be as high as 58 kg.cm/cm.

Further, the sample was molded by the 0.1 oz injection molding machineby means of mold B, and the molded product showed a tensile strength ashigh as 2,220 kg/cm².

EXAMPLES 2 to 8

The operation was conducted in the same manner as in Example 1 exceptthat the types and feeding ratios of the starting materials and thepolymerization conditions were changed as shown in Table 1. Thepolymerization conditions, etc. in Examples 1 to 8 and the results ofmeasurements of various physical properties are listed in Table 1.

EXAMPLE 9

Into a glass tube equipped with a stirrer, a nitrogen inlet and a vacuumport, 49.1 (0.163 mol) of ##STR93## 27.0 g (0.163 mol) of ##STR94## 39.3g (0.284 mol) of ##STR95## and 5.6 g (0.041 mol) of ##STR96## werecharged, and the polymerizer was flushed with nitrogen under vacuum.Then, 83.0 g (0.813 mol) of acetic anhydride was added thereto. Thesystem was heated to 140° C. under stirring and maintained at 140° C.for one hour. Then, it was heated to 275° C. over a period of 1.5 hours.When the temperature reached 275° C., vacuuming was started. Thepressure was reduced to 10 mmHg in one hour and then from 10 mmHg to 0.3mmHg over a period of 1.5 hours. Polymerization was conducted under 0.3mmHg for 30 minutes, whereupon the torque was sufficiently high, and thepolymerization was terminated.

Then, the system was left to stand still to let the pressure return to anormal level, and the polymer was discharged from the bottom of theglass tube. The dischargeability was excellent. The polymer was formedinto chips and then dried under vacuum at 120° C. overnight. Thispolymer had η_(inh) of 1.17 and a melt viscosity of 750 poise at 275° C.

With this polymer, r₁ =0.80. FIG. 13 shows the NMR chart after aminedecomposition which was used for obtaining r₁ =0.80. Further, variousmechanical properties were as shown in Table 2.

Further, FIG. 11 shows a chart of various vibrons including Example 9.The one shown in the Figure is that of Example 9. Vibron T₁ is 175° C.,and T₂ was 250° C. Thus, a=T₂ -T₁ =75° C., which is substantially smallas compared with the conventional polymer having the same compositionalratio.

The mechanical properties were measured with respect to a specimenmolded by the 0.1 oz injection molding machine by means of mold B. Amongthe mechanical properties, especially the tensile strength was as highas 2480 kg/cm². Also the elongation at breakage was 4.6% which issubstantially high as compared with Comparative Examples with the samecompositional ratio. Namely, this indicates that the polymer of thepresent invention is fairly tough, while those having an elongation atbreakage of not higher than 3% tend to be brittle, as mentioned above.

Further, as compared with the Comparative Examples, the melt viscosityis low relative to η_(inh).

The temperature dependency of the melt viscosity was small with 750poise at 275° C. and 430 poise at 290° C.

EXAMPLES 10 to 16

The operation was conducted in the same manner as in Example 9 exceptthat the types and feeding ratios of the starting materials and thepolymerization conditions were changed as shown in Table 2. Namely,after acetylation, the temperature was raised to the polymerizationtemperature over a period of 1.5 hours, and when the temperature reachedthe polymerization temperature, vacuuming was started.

The pressure was reduced to 10 mmHg in one hour and then to a level ofless than 1 mmHg over a period of 1.5 hours.

Accordingly, in a case where the polymerization time was 2.5 hours ormore, the final pressure was lower than 1 mmHg, and in a case where thepolymerization time was less than 2.5 hours, the pressure at that timewas the final pressure, which was 1 mmHg or higher.

The polymerization conditions in Examples 9 to 16 and the results ofmeasurement of various physical properties are shown in Table 2.

Examples 13 and 14 will be described in further detail.

In Example 13, the polymerization was conducted by using the same glasstube as in Example 9 under the conditions as identified in Table 2.

FIG. 13 shows the NMR chart used for the determination of r₃ =0.78.η_(inh) =1.36. The melt viscosity at 275° C. was 1580 poise, and thetensile strength of the molded specimen at 275° C. was as high as 2580kg/cm². Also the elongation at breakage was as high as 4.4%, thusindicating toughness.

Example 14 was conducted in a scale 50 times the scale of Example 13using a SUS 20 l autoclave. With this polymer, r₃ =0.78, η_(inh) =1.32,and the melt viscosity at 275° C. was 1500 poise. Molding was conductedby varying the temperature, whereby the results as shown in Table 1 wereobtained. These results indicate that the elastic modulus, strength andelongation are higher as the molding temperature is lower. Further, ASTMspecimens were prepared, and the Izod impact strength and HDT weremeasured. Further, the vibron chart of this polymer is shown in FIG. 11.T₁ =180 and T₂ =259° C. Thus, a was as small as 79° C.

Further, FIG. 12 shows a DSC chart. A distinct melting point was shownwith T_(m) =260.4° C.

70 Parts by weight of this polymer and 30 parts by weight of glass fiberwere kneaded by a twin screw kneader. Then, ASTM specimens wereprepared, and HDT was measured in the same manner as described above.

FIG. 14 shows a NMR chart after amine decomposition for determining r₃in Example 12.

EXAMPLE 17

Into a glass tube equipped with a stirrer, a nitrogen inlet and a vacuumport, 29.3 g (0.161 mol) of ##STR97## and 22.2 g (0.161 mol) of##STR98## were charged, and the glass tube was flushed with nitrogenunder vacuum. Then, while supplying nitrogen, the system was heatedunder stirring. The system became transparent at 170° C., and whenreached 180° C., it was maintained at that temperature for 2 hours.Then, it was heated to 200° C. and maintained for one hour. As thereaction proceeded, the system became opaque and was finally solidified.

Then, 44.4 g (0.322 mol) of ##STR99## 26.7 g (0.161 mol) of ##STR100##and 82.1 g (0.805 mol) of acetic anhydride were added thereto, andacylation was conducted for one hour at 140° C. under stirring. Then,the system was heated to 275° C. over a period of 1.5 hours, and thenvacuuming was started. The pressure was reduced to 10 mmHg in one hourand then from 10 mmHg to 0.3 mmHg over a period of 1.5 hours. Whenpolymerization was conducted under 0.3 mmHg for 2 hours, the torquebecame sufficiently high, and therefore, the polymerization wasterminated.

Then, the system was left to standstill to let the pressure return to anormal level, and the polymer was discharged from the bottom of thepolymerizer. The dischargeability was excellent.

The polymer was formed into chips and dried at 120° C. overnight.

This polymer had η_(inh) of 1.00 dl/g, and the melt viscosity was 730poise when γ=10³ sec⁻¹ at 275° C.

Then dumbbell specimens were prepared by the 0.1 oz injection moldingmachine (mold: B), and the mechanical properties were measured. Theelongation at breakage was 3.3%, and the tensile strength was 2000kg/cm², and the modulus of elasticity was 9.0×10⁴ kg/cm².

With this polymer, r₁ =0.82, and r₂ =0.82.

EXAMPLE 18

Into a glass tube equipped with a stirrer, a nitrogen inlet and a vacuumport, 29.3 g (0.161 mol) of ##STR101## and 86.9 g (0.483 mol) of##STR102## were charged, and the glass tube was flushed with nitrogenunder vacuum. Then, while supplying nitrogen, the system was heatedunder stirring. The system became transparent at 200° C. and maintainedfor 2 hours for the reaction.

Then, 26.7 g (0.161 mol) of ##STR103## and 20.5 g (0.201 mol) of aceticanhydride were added

thereto, and the mixture was maintained at 140° C. for one hour understirring. Then, the temperature was raised to 275° C. over a period of1.5 hours, and vacuuming was started. The pressure was reduced to 10mmHg in one hour and then from 10 mmHg to 0.3 mmHg over a period of 1.5hours. When polymerization was conducted under 0.3 mmHg for 3 hours, thetorque became sufficiently high, and the polymerization was terminated.

Then, the system was left to stand still to let the pressure return to anormal level, and the polymer was discharged from the bottom of theglass tube.

The polymer was formed into chips and dried at 120° C. overnight. Thispolymer had η_(inh) of 1.03 dl/g and a melt viscosity of 700 poise whenγ=10³ sec⁻¹ at 275° C.

Then, dumbbell specimens were prepared by the 0.1 oz injection moldingmachine (mold B), and the mechanical properties were measured, wherebythe elongation at breakage was 3.4%, the tensile strength was 2020kg/cm², and the modulus of elasticity was 9.5×10⁴ kg/cm². With thispolymer, r₁ =0.82 and r₂ =0.82.

    TABLE 1        Polymerization  Ex-    Final  am-    pres- Dis- ple Starting materials      Temp. Time sure charge- No. (6), (7) (8) (9-1), (10-1) (16) (°C.)      hr. min. (mmHg) ability                 1      ##STR104##      ##STR105##      ##STR106##      82.1 g(0.81mol) 275 1 55 6 ◯      2     ##STR107##      ##STR108##      ##STR109##      75.2 g(0.74mol) 275 6 00 0.2 ◯      3     ##STR110##      ##STR111##      -- 65.3 g(0.64mol) 275 4 00 0.2 ◯      4     ##STR112##      ##STR113##      ##STR114##      86.7 g(0.85mol) 290 0 40 25 ◯      5     ##STR115##      ##STR116##      ##STR117##      5.1 g(0.05mol) 290 3 30 0.25 ◯      6     ##STR118##      ##STR119##      ##STR120##      82.1 g(0.81mol) 275 1 15 20 ◯   7 Same as Example 1 Same as     Example 1 Same as Example 1 Same 275 4 00 0.15 ◯     as     Exam-     ple 1 8 Same as Example 1 Same as Example 1 Same as Example 1     Same 290 1 40 6 ◯     as     Exam-     ple 1        500 MHz - .sup.1 H-NMR of polymers Amine decomposition - .sup.1 H-NMR      Ratios of polymer Ratios of chains of  Ratios of polymer   Example     units (molar ratios) (3-1) and (3-2)  units (molar ratios) Ratios of     chains of (3-4) No. [1] [2] [3] [3-1]/[3] × 100 [3-2]/[3] ×     100 r.sub.1 [1] [2] [3] [3]-[3-4]/[3] × 100 [3-4]/[3]  × 100 r     .sub.2       1 20 20 80 60 40 0.75 20 20 80 61 39 0.78 2 25 25 75 53 47 0.75 25 25     75 52 48 0.72 3 34 34 66 42 58 0.74 33 33 67 43 57 0.74 4 16.5 16.5 83.5     66 34 0.77 17 17 83 65 35 0.76 5 25 26 75 55 45 0.81 25 25 75 56 44 0.85     6 20 20 80 62 38 0.82 20 20 80 62 38 0.82 7 20 19 80 61 39 0.77 20 20 79     61 39 0.78 8 20 20 80 61.5 38.9 0.80 20 20 80 61 39 0.78            Mechanical properties (Tensile    Solubility Melt viscosity     (poise)  properties) 0.1 oz (Mold A)   in Temperature Molding Elastic     Elongation  Example η.sub.inh hexafluoro- 200 220 260 275 290 temp     modulus × Strength at breakage HDT No. (dl/g) isopropanol (°     C.) (°C.) (°C.) (°C.) (°C.) (°C.)     10.sup.-4 (kg/cm.sup.2) (kg/cm.sup.2) (%) (°C.)       1 0.98 ◯ -- -- 5,600 830 520 275 7.0 1,320 3.7 197     290 7.0 1,280 3.5 2 0.91 ◯ -- --   580 310 -- 250 7.6 1,330     3.5 170         275 7.6 1,230 3.0 3 0.54 ◯ 1,450 230 -- --     -- -- -- -- -- 113 4 0.75 ◯ -- -- -- 1,000   110 275 6.6     1,250 3.3 213         290 6.4 1,160 2.9 5 0.64 ◯ -- -- -- --     -- -- -- -- -- 162 6 1.07 ◯ -- -- -- 560 210 275 7.9 1,380     3.6 138 7 1.53 ◯ -- -- -- 1,850   1,150   290 6.4 1,370 4.7     -- 8 1.31 ◯ -- -- -- -- 700 290 7.7 1,230 3.4 --        Vibron data    T.sub.1 (Temp. T.sub.2 (Temp.    Example under 3     × 10.sup.10 under 5 × 10.sup.9 a = T.sub.2 - T.sub.1 Liquid     Crystallinity No. dyne/cm.sup.2) (°C.) dyne/cm.sup.2) (°C.)      (°C.) crystallinity DSC X-ray       1 224 270 46 ◯ T.sub.m = 265.7° C. Described     T.sub.c = 223.8° C. above 2 185 240 55 ◯ -- -- 3 118     189 71 ◯ -- -- 4 221 288 67 ◯ -- -- 5 174 249 75     ◯ -- -- 6 165 243 78 ◯ -- -- 7 -- -- -- .largecir     cle. -- -- 8 -- -- -- ◯ -- --

    TABLE 2        Polymerization      Final Dis- Ex. Starting materials Temp. Time     pressure charge- No. (6), (7) (8) (9-1), (10-1) (9-2), (10-2) (16)     (°C.) hr min (mmHg) ability      9     ##STR121##      ##STR122##      ##STR123##      ##STR124##      83.0 g(0.813 mol) 275 3 00 0.2 ◯      10     ##STR125##      ##STR126##      ##STR127##      ##STR128##      87.1 g(0.853 mol) 275 2 15 3.5 ◯      11     ##STR129##      ##STR130##      ##STR131##      ##STR132##      87.1 g(0.853 mol) 275 1 40 6 ◯      12     ##STR133##      ##STR134##      ##STR135##      ##STR136##      83.0 g(0.813 mol) 275 4 00 0.19 ◯      13     ##STR137##      ##STR138##      ##STR139##      ##STR140##      83.0 g(0.813 mol) 275 3 30 0.15 ◯      14     ##STR141##      ##STR142##      ##STR143##      ##STR144##      4111 g(40.3 mol) 275 4 20 0.5 ◯      15     ##STR145##      ##STR146##      ##STR147##      -- 83.0 g(0.813 mol) 275 1 15 9 ◯      16     ##STR148##      ##STR149##      ##STR150##      ##STR151##      86.6 g(0.85 mol) 275 3 45 0.3 ◯        Amine decomposition .sup.1 H-NMR      Example Ratios of polymer units     (molar ratios) No. [1] [2] [3] [5] [4]/[1] + [4] [5]/[3] + [5] r.sub.3     [4]-[ 4-4]/[4] × 100 [4-4]/[4] ×      100                            9 20 20 75 5 0.80 0.063 0.80 61.5 38.5     10 19.2 19.2 76.9 3.8 0.81 0.047 0.78 62 38 11 16 16 80 4 0.84 0.048     0.82 68 32 12 20 20 70 10 0.80 0.125 0.80 61.5 38.5 13 20 20 78 2 0.80     0.025 0.78 61 39 14 20 20 78 2 0.80 0.025 0.78 61 39 15 20 20 75 5 0.80     0.063 0.75 60 40 16 25 25 71.5 3.5 0.75 0.047 0.80 54.5 45.5           Mechanical properties       Tensile properties (0.1 oz  Tensile     properties (0.1 oz       Mold B)  Mold C)     Elastic  Elonga-  Elastic  E     longa- Thermal properties    Melt viscosity Molding modulus ×     tion at  modulus ×  tion at Vicat  Melting Liquid Example η.sub     .inh (poise) temp. 10.sup.-4 Strength breakage Izod 10.sup.-4 Strength     breakage softening  point crystal- No. (dl/g) 275° C. 290°     C. (°C.) (kg/cm.sup.2) (kg/cm.sup.2) (%) (kg · cm/cm)     (kg/cm.sup.2) (kg/cm.sup.2) (%) point (°C.) HDT (°C.)     (°C.) linity      9 1.17 750 430 275 9.4 2,480 4.6 -- 9.4 2,180 4.3 145 -- -- .largecircle     . 10 1.12 560 310 275 8.9 2,520 3.8 --    -- -- -- ◯ 11 1.17      430 280 8.0 2,210 3.7 --    182 -- -- ◯ 12 1.04   275 11.1     >3,200  >6.5  --    105 -- -- ◯ 13 1.33 1580  760 275 9.2     2,580 4.4 -- 8.1 2,300 5.0 173 -- -- ◯ 14 1.32 1500  750 275     9.8 2,500 4.3 70 8.7 2,100 4.2 -- 125 260.4 ◯ Include    290     9.6 2,410 4.0 --    173 -- 30 wt %    300 7.0 2,360 3.7 --    -- --     glass  -- -- 275 -- -- -- --    -- 190 -- ◯ fiber 15 1.17     680 440 275 9.3 2,630 5.0        ◯ 16    275 8.4 2,500 4.2          ◯

FIG. 6 shows vibron charts of Examples 1 to 4. Each of them is a liquidcrystalline polyester comprising ##STR152##

From the comparison of Examples 2 and 5, it is apparent that when R¹ is##STR153## r₁ and r₂ tend to be small as compared with the case where R¹is ##STR154##

COMPARATIVE EXAMPLES 1 and 2

Polymers were prepared in accordance with the method disclosed inJapanese Examined Patent Publication No. 18016/1981.

In Comparative Example 1, polymerization was conducted at a ratio ofpolyethylene terephthalate/p-acetoxybenzoic acid=30/70. (molar ratio).

In Comparative Example 2, polymerization was conducted at a ratio ofpolyethylene terephthalate/p-actoxybenzoic acid=20/80 (molar ratio).

The compositional ratios of the formed polymers ##STR155## are shown inTable 3.

COMPARATIVE EXAMPLES 3 and 4

Polymers were prepared in accordance with the method disclosed inJapanese Unexamined patent Publication No. 186527/1985.

The compositional ratios of the formed polymers of Examples 3 and 4##STR156## are shown in Table 3.

COMPARATIVE EXAMPLE 5

A two step polymerization was conducted in accordance with JapaneseUnexamined Patent Publication No. 26632/1989, and the compositionalratios are shown in Table 3.

COMPARATIVE EXAMPLE 6

A polymer was prepared in accordance with Example 1 of JapaneseUnexamined Patent Publication No. 45524/1990.

Various physical properties of Comparative Examples 1 to 6 are shown inTable 3. In each of Comparative Examples 1 to 6, R¹ of (1) is ##STR157##

With respect to HDT, the operation was conducted in the same manner asin Example.

The polymers of Comparative Examples 1, 2, 5 and 6 could not bedissolved in hexafluoroisopropanol.

In Comparative Examples 2 and 4, the mechanical properties were improvedwhen the polymers were molded at a high temperature.

In each of Comparative Examples 1 to 6, a (T₂ -T₁) exceeded 80° C.

In each case, the tensile strength and the elongation at breakage werelow. Especially, the elongation at breakage was as low as not higherthan 3%.

In Comparative Examples 2, 5 and 6, the melt viscosity (at 275° C.) wasvery high. Particularly in Comparative Examples 5 and 6, the meltviscosity was high relative to η_(inh). In Comparative Example 2,η_(inh) was not measured, since insoluble matters were present, but fromthe melt viscosity, it was apparent that the physical properties wereinferior.

The scattering angles of the peaks in the X-ray data of ComparativeExample 5 are shown in Table 3.

As compared with Example 1, the crystal lattice in the fiber directionis slightly large, and the packing distance between molecules isslightly large.

The data used for determining r₁ and r₂ in Comparative Example 2 areshown in FIGS. 9 and 10, respectively. From FIG. 9, it is evident thatthe proportion of (13) is high. From FIG. 10, it is evident that thereis a substantial amount of independent HOCH₂ CH₂ OH i.e. there is asubstantial amount of a unit of ##STR158## and/or ##STR159## there is asmall amount of structure of ##STR160##

COMPARATIVE EXAMPLE 7

A polymer was prepared in accordance with the method disclosed inJapanese Examined Patent Publication No. 18016/1981. Namely,polyethylene terephthalate, p-actoxybenzoic acid and m-acetoxybenzoicacid were used as starting materials so that the final ratios of thepolymer units would be the same as in Example 13 (see Table 4).

COMPARATIVE EXAMPLE 8

A polymer was prepared in accordance with the method disclosed inJapanese Unexamined Patent Publication No. 285916/1987. Namely,polyethylene terephthalate, acetic anhydride, p-hydroxybenzoic acid andm-hyroxybenzoic acid were used as starting materials so that the finalratios of polymer units would be the same as in Example 13 (see Table4).

COMPARATIVE EXAMPLE 9

A polymer was prepared in accordance with the method disclosed inJapanese Unexamined Patent Publication No. 121095/1977. Namely,polyethylene terephthalate, , p-hydroxybenzoic acid, m-hyroxybenzoicacid and diphenyl carbonate were used as starting materials so that thefinal ratios of polymer units would be the same as in Example 13 (seeTable 4).

COMPARATIVE EXAMPLE 10

A polymer was prepared in accordance with the method disclosed inJapanese Unexamined Patent Publication No. 186525/1985, so that thefinal ratios of polymer units would be the same as in Example 13 (seeTable 4).

COMPARATIVE EXAMPLE 11

Two step polymerization was conducted by an addition of m-acetoxybenzoicacid in accordance with the method disclosed in Japanese UnexaminedPatent Publication No. 26632/1989. The ratios of polymer units are shownin Table 4.

    __________________________________________________________________________    500 MHz - .sup.1 H-NMR of polymers                                                                              Amine decomposition - .sup.1 H-NMR          Compara-                                                                            Ratios of polymer           Ratios of polymer                           tive  units    Ratios of chains of                                                                              units                                       Example                                                                             (molar ratios)                                                                         (3-1) and (3-2)    (molar ratios)                                                                         Ratios of chains of (3-4)          No.   [1]                                                                              [2]                                                                              [3]                                                                              [3-1]/[3] × 100                                                                 [3-2]/[3] × 100                                                                 r.sub.1                                                                          [1]                                                                              [2]                                                                              [3]                                                                              [3]-[3-4]/[3] × 100                                                              [3-4]/[3] ×                                                             100     r.sub.2           __________________________________________________________________________    1     30 30 70 59      41      1.24                                                                             30 30 70 61       39      1.34              2     20 20 80 69      31      1.11                                                                             20 20 80 70       30      1.18              3     25 24 75 59      41      0.96                                                                             25 24 75 61       39      1.00              4     21 20 80 63.5    36.5    0.91                                                                             21 20 80 65.5     34.5    0.95              5     20 20 80 65      35      0.93                                                                             20 20 80 67       33      1.02              6     20 20 80 65      35      0.93                                                                             20 20 80 66       34      0.97              __________________________________________________________________________                                               Mechanical properties                                                         (Tensile                           Compara-       Solubility                                                                            Melt                properties) (0.01 oz mold A)       tive           in      viscosity    Molding                                                                              Elastic                            Example  ηinh                                                                            hexafluoro-                                                                           (poise)      temp   modulus    Strength                No.      (dl/g)                                                                              isopropanol                                                                           275° C.                                                                       290° C.                                                                      (°C.)                                                                         × 10.sup.-4                                                             (kg/cm.sup.2)                                                                            (kg/cm.sup.2)           __________________________________________________________________________    1        --    Insoluble                                                                             --     --    275    5.4        1020                    2        Insol-                                                                              Insoluble                                                                             1,800  --    275    3.5         570                             uble                       300    4.5         870                    3        0.91  --      --     --    275    6.7        1210                    4        0.95  --      --     --    275    7.2        1220                                                        300    7.2        1250                    5        0.98  Insoluble                                                                             1,450  --    275    6.9        1230                    6        1.05  Insoluble                                                                             1.,620 --    275    6.7        1180                    __________________________________________________________________________                Mechanical properties                                                                           Vibron data                                                 (Tensile properties)                                                                            T.sub.1 (Temp.                                                                         T.sub.2 (Temp.                         Compara-    (0.01 oz mold A)  under    under                                  tive        Elongation        3 × 10.sup.10                                                                    5 × 10.sup.9                                                                     a =                           Example     at breakage                                                                              HDT    dyne/cm.sup.2)                                                                         dyne/cm.sup.2)                                                                         T2 - T1                       No.         (%)        (°C.)                                                                         (°C.)                                                                           (°C.)                                                                           (°C.)                                                                          X-ray                 __________________________________________________________________________    1           3.0        --     125      223      98      --                    2           2.3        --     101      288      187     Orienta-                          2.6                                         tion too                                                                      low to be                                                                     distinct              3           3.0         90    128      221      93      --                    4           2.8        120    138      236      98      --                                3.0                                                               5           2.9        171    202      285      83      Meridional                                                                    direction:                                                                    14.82°                                                                 27.92°                                                                 43.4°                                                                  Equatorial                                                                    20.16°:        6           2.7        152    183      279      96      --                    __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Compara-                                                                      tive    Amine decomposition .sup.1 H-NMR                                      Example Ratios of polymer units                                               No.     [1] [2]  [3] [5] [4]/[1] + [4]                                                                          [5]/[3] + [5]                                                                         [4]-[4-4]/[4] × 100                                                                r.sub.3                  __________________________________________________________________________    7       20  20   78  2   0.80     0.025   72         1.29                     8       20  20   78  2   0.80     0.025   71         1.22                     9       20  20   78  2   0.80     0.025   70         1.18                     10      20  20   78  2   0.80     0.025   66         0.97                     11      20  20   78  2   0.80     0.025   67         1.02                     __________________________________________________________________________                       Tensile properties (0.1 oz                                                                           Tensile properties (0.3 oz                             Mold B)                Mold C)                             Compara-           Elastic   Elonga-      Elastic   Elonga-                   tive       Melt viscosity                                                                        modulus   tion at      modulus   tion at                   Example                                                                             ηinh                                                                           poise   × 10.sup.-4                                                                  Strength                                                                           breakage                                                                           a (°C.)                                                                    HDT × 10.sup.-4                                                                  Strength                                                                           breakage                  No.   (dl/g)                                                                             275° C.                                                                    290° C.                                                                    (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (%)  T.sub.2 - T.sub.1                                                                 (°C.)                                                                      (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (%)                       __________________________________________________________________________    7     Insoluble                                                                          1800                                                                              470 6.8  1560 2.7  105                                         8     Insoluble                                                                          1600                                                                              520 7.4  1720 2.8  100                                         9     Insoluble                                                                          1400                                                                              560 7.6  1780 2.8  102                                         10    1.32 --  --  7.9  1980 3.2   94 90  7.3  1,730                                                                              3.0                       11    --   1700                                                                              600 7.8  1920 3.1   97                                         __________________________________________________________________________

EXAMPLE 19

Polymerization was conducted in the same manner as in Example 1 (threetimes in scale). After a polymerization time of 2 hours and 40 minutes(from the initiation of vacuuming), the polymerization was terminated,and the polymer was discharged. The dischargeability was excellent.η_(inh) =1.32.

This polymer was molded by the 0.1 oz injection molding machine by meansof mold A or B and by the 0.3 oz injection molding machine by means ofmold C. The respective values are shown in Table 5.

Further, the same polymer as in Example 1 was prepared and molded by the0.1 oz injection molding machine by means of mold B and by the 0.3 ozinjection molding machine by means of mold C.

Further, polymers of Comparative Examples 1 to 6 were also molded by the0.1 oz injection molding machine by means of mold B and by the 0.3 ozinjection molding machine by means of mold C.

EXAMPLE 20

Using a 20 l autoclave, polymerization was conducted in a scale 50 timesthe scale of Example 1. The results are shown in Table 5.

EXAMPLE 21

Polymerization was conducted with the same composition as in Example 6for a polymerization time of 2 hours and 30 minutes. η_(inh) was 1.25,r₁ =0.78 and r₂ =0.80.

This polymer was molded by the 0.1 oz injection molding machine (moldA), whereby the tensile strength was 1610 kg/cm² and the elongation atbreakage was 5.0%.

EXAMPLE 22

Into a glass tube equipped with a stirrer, a nitrogen inlet and a vacuumport, 29.3 g (0.161 mol) of ##STR161## 86.9 g (0.483 mol) of ##STR162##and 26.7 g (0.161 mol) of ##STR163## were charged, and the glass tubewas flushed with nitrogen under vacuum. Then, while supplying nitrogen,the system was heated under stirring. The system became transparent at200° C. and maintained for 2 hours for the reaction.

Then, 20.5 g (0.201 mol) of acetic anhydride were added thereto.

Further operation was conducted in the same manner as in Example 18except that the total polymerizing time was 3 hours. Thedischargeability of polymer was excellent. This polymer had η_(inh) of1.13 dl/g. Then dumbbell specimens were prepared by the 0.1 oz injectionmolding machine (mold: B), and the mechanical properties were measured.The tensile strength was 2040 kg/cm², and the modulus of elasticity was9.5×10⁴ kg/cm².

                                      TABLE 5                                     __________________________________________________________________________                          Tensile properties (0.1 oz                                                                   Tensile properties                                             Mold A)        (0.1 oz Mold B)                                   Melting      Elastic   Elonga-                                                                            Elastic                                           viscosity                                                                             Molding                                                                            modulus   tion at                                                                            modulus                                  ηinh poise   temp × 10.sup.-4                                                                  Strength                                                                           breakage                                                                           × 10.sup.-4                             (dl/g)                                                                            275° C.                                                                    290° C.                                                                    (°C.)                                                                       (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (%)  (kg/cm.sup.2)                            __________________________________________________________________________    Example                                                                       No.                                                                           19   1.32                                                                              1,100   275  6.8  1,340                                                                              3.9  9.3                                      20   0.98*                                                                               830*                                                                            520*                                                                              275* 7.0* 1,320*                                                                             3.7* 9.2                                      Compar-                                                                       ative                                                                         Example                                                                       No.                                                                           1    --   --*    275* 5.4* 1,020*                                                                             3.0*                                          2    Insol-                                                                            1,800*  275* 3.5*   570*                                                                             2.3*                                               ble*                                                                     3    0.91*                                                                             --      275* 6.7* 1,210*                                                                             3.0*                                          4    0.95*                                                                             --      275* 7.2* 1,220*                                                                             2.8* 9.1                                      5    0.98*                                                                             1,450*  275* 6.9* 1,230*                                                                             2.9* 7.7                                      6    1.05*                                                                             1,620*  275* 6.7* 1,180*                                                                             2.7*                                          __________________________________________________________________________                Tensile properties                                                                      Tensile properties (0.3 oz                                          (0.1 oz Mold B)                                                                         Mold C)                                                                  Elonga-                                                                            Elastic   Elonga-                                                        tion at                                                                            modulus   tion at  Izod                                             Strength                                                                           breakage                                                                           × 10.sup.-4                                                                  Strength                                                                           breakage                                                                           HDT (kg · cm/                               (kg/cm.sup.2)                                                                      (%)  (kg/cm.sup.2)                                                                      (kg/cm.sup.2)                                                                      (%)  (°C.)                                                                      cm)                                  __________________________________________________________________________           Example                                                                       No.                                                                           19   2,140                                                                              3.7  8.0  2,120                                                                              4.2                                                  20   2,220                                                                              3.5  8.2  2,040                                                                              4.0  197*                                                                              58                                          Compar-                                                                       ative                                                                         Example                                                                       No.                                                                           1                             73                                              2                             152 18                                          3                              90*                                            4    1,830                                                                              2.8  7.0  1,520                                                                              3.0  120*                                                                              33                                          5    1,730                                                                              2.9  5.7  1,460                                                                              3.0  171*                                                                              30                                          6              6.4  1,350                                                                              2.8  152*                                                                              27                                   __________________________________________________________________________     *Data disclosed in Tables or in the description.                         

The absolute values for the mechanical properties (particularlystrength) substantially vary depending upon the type of the moldingmachine or the type of the mold. However, the relative comparison amongvarious polymers can adequately be made, and there is no doubt that theproducts of the present invention exhibit superior physical propertiesas compared with the products of Comparative Examples.

As described in the foregoing, the liquid crystalline polyester of thepresent invention is superior in the mechanical properties and thermalproperties to conventional polyesters having the same composition andthe same compositional ratio, as the sequence is alternately bettercontrolled. Namely, it has high strength and high elongation andexhibits better physical properties as the molding temperature is lower.Further, since the crystallinity is high, the melting point is distinct,and reinforcing effects with e.g. glass fibers will be obtained.Further, HDT is high and yet it is flowable at a low temperature inspite of its heat resistance. Therefore, it has a merit that thepolymerization temperature can be lowered. Further, it has a merit thateven when the polymerization temperature is low, it can be readilywithdrawn from the bottom of the glass tube.

Further, the liquid crystalline polyester of the present invention showsan optical anisotropy in its molten phase. Especially, once it starts tomelt, there will be no substantial solid portion simply by raising thetemperature slightly over the melt initiation temperature, and almostall will be a primary liquid crystal state. Thus, it has a feature thatfluidity is far better than that of the conventional polyesters.

By virtue of the high fluidity, the liquid crystalline polyester of thepresent invention is suitable for e.g. precision molded products. Forexample, it is useful for automobile parts, parts of informationmaterials such as compact discs or flexible discs or pats of electronicmaterials such as connectors or IC sockets.

It is also useful in the form of films or fibers, and is particularlysuitable for films.

We claim:
 1. A liquid crystalline polyester consisting essentially ofdicarboxylic acid units of the following formula (1): ##STR164## whereinR¹ is bivalent aromatic hydrocarbon group having from 6 to 18 carbonatoms, diol units of the following formula (2):

    --OCH.sub.2 CH.sub.2 O--                                   (2)

and p-oxybenzoic acid units of the following formula (3): ##STR165##wherein (i) where moles of said units (1), (2) and (3) are representedby [1], [2] and [3], respectively, they satisfy the following formula(I): ##EQU84## (ii) the sequence of the units satisfies the followingformula

    ≦ r.sub.1 ≦0.88 or 0≦r.sub.2 ≦0.88

wherein r₁ is a sequence forming ratio which is defined by formula (II):##EQU85## and r₂ is a sequence forming ratio which is defined by formula(III): ##EQU86## where [3-1] represents the mole of p-oxybenzoic acidunits having on their --O-- side a further p-oxybenzoic acid,represented by the underlined portion of formula (3-1): ##STR166## and[3-4] represents the mole of p-oxybenzoic acid units having on their##STR167## side a diol unit of formula (2), represented by theunderlined portion of the formula (3-4): ##STR168## each among thep-oxybenzoic acid units of the formula (3), and (iii) the viscosity of asolution of the polyester as measured inp-chlorophenol/o-dichlorobenzene (30° C., concentration: 0.5 g/dl) is atleast 0.4 dl/g.
 2. The liquid crystalline polyester according to claim1, wherein r₁ and r₂ are simultaneously within the respective ranges of0>r₁ ≦0.88 and 0≦r₂ ≦0.88.
 3. The liquid crystalline polyester accordingto claim 1, wherein the molar ratio of the units of the formula (1) andthe units of the formula (3) is within a range of the formula: ##EQU87##4. A liquid crystalline polyester comprising dicarboxylic acid units ofthe following formula (1): ##STR169## wherein R¹ is a bivalent aromatichydrocarbon group having from 6 to 18 carbon atoms, diol units of thefollowing formula (2):

    --OCH.sub.2 CH.sub.2 O--                                   (2)

and oxybenzoic acid units of the following formula (4): ##STR170##wherein (i) where the moles of said units (1), (2) and (4) arerepresented by [1], [2] and [4], respectively, they satisfy thefollowing formula (IV): ##EQU88## (ii) where among the oxybenzoic acidunits, oxybenzoic acid units having on their ##STR171## side a diol unitof the formula (2), are represented by the underlined portion of theformula (4--4): ##STR172## and the moles of (4--4) are represented by[4--4], r₃ as defined by the following formula (V): ##EQU89## satisfies0≦r₃ ≦0.88, and (iii) the viscosity of a solution of the polyester asmeasured in p-chlorophenol/o-diclorobenzene (30° C., concentration: 0.5g/dl) is at least 0.4 dl/g.
 5. The liquid crystalline polyesteraccording to claim 4, wherein the molar ratio of the units of theformula (1) and the units of the formula (4) is within a range of theformula: ##EQU90##
 6. The liquid crystalline polyester according toclaim 4, wherein the oxybenzoic acid units of the formula (4) comprisep-oxybenzoic acid units of the formula (3): ##STR173## and m-oxybenzoicacid units of the formula (5): ##STR174## and where the moles of saidunits (3) and (5) are represented by [3] and [5], respectively, theysatisfy the following formula (VI): ##EQU91##